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EP0356712B1 - Schlagfesten Kautschuk enthaltende Schmelzklebstoffzusammensetzungen für die Buchbinderei - Google Patents

Schlagfesten Kautschuk enthaltende Schmelzklebstoffzusammensetzungen für die Buchbinderei Download PDF

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Publication number
EP0356712B1
EP0356712B1 EP89113908A EP89113908A EP0356712B1 EP 0356712 B1 EP0356712 B1 EP 0356712B1 EP 89113908 A EP89113908 A EP 89113908A EP 89113908 A EP89113908 A EP 89113908A EP 0356712 B1 EP0356712 B1 EP 0356712B1
Authority
EP
European Patent Office
Prior art keywords
hot melt
weight
adhesive
mpa
melt adhesive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP89113908A
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English (en)
French (fr)
Other versions
EP0356712A1 (de
Inventor
Thomas P. Flanagan
Paul Puletti
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
National Starch and Chemical Investment Holding Corp
Original Assignee
National Starch and Chemical Investment Holding Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
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Publication of EP0356712A1 publication Critical patent/EP0356712A1/de
Application granted granted Critical
Publication of EP0356712B1 publication Critical patent/EP0356712B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42C—BOOKBINDING
    • B42C9/00—Applying glue or adhesive peculiar to bookbinding
    • B42C9/0006—Applying glue or adhesive peculiar to bookbinding by applying adhesive to a stack of sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S156/00—Adhesive bonding and miscellaneous chemical manufacture
    • Y10S156/908—Laminating sheet to entire edge of block and both adjacent opposite surfaces, e.g. bookbinding

Definitions

  • thermoplastic rubbery copolymers comprising domains of polystyrene endblocks and rubbery butadiene midblocks are available.
  • the various copolymers have been suggested for different end uses including some grades which are recommended for use in moldings or extrusions (e.g. footwear, automotive, hose, etc.) while other grades are recommended as adhesives, coatings or sealants.
  • GB-A- 1 592 358 From GB-A- 1 592 358 a process for bookbinding, wherein the pages are joined together by means of a hot melt adhesive is known.
  • an hot-melt adhesive composition consisting of 100 parts by wt of a styrene-butadiene-styrene block copolymer, block molecular weights 12,000-56,000-12,000, 100 parts by wt of glycerol ester of perhydrogenated rosin (Foral 85ex Hercules (non-terminal-block-compatible resin)), 100 parts by wt of paraffin wax (softening point 58-60 °C) and 5 parts by wt of a stabilizer (zinc dibutyl dithiocarbamate).
  • the present invention is directed to hot melt adhesive compositions suitable for bookbinding applications comprising tackifying resins, at least one wax diluent, a stabilizer and a substantially radial styrene-butadiene block copolymer, the copolymer having a styrene content greater than about 35% by weight, a modulus at 300% elongation of at least 4.5 MPa and a solution viscosity less than about 1000 mPa.s (1000 cps) as defined in the claims.
  • the resultant toughened hot melt adhesives of the invention are excellent in the bookbinding field where, due in part to the lower viscosity of the copolymer, they can be formulated using lower levels of the copolymer and yet achieve comparable or better results than are found in conventional book binding hot melts.
  • the use of the specific copolymers described herein permits easy formulation of bookbinding adhesives with Fischer-Tropsch waxes whereas use of Fischer-Tropsch wax with heretofor available block copolymers resulted in unacceptable brittleness and a tendency toward significant stress cracking.
  • block copolymers described herein may also be used to formulate hot melt adhesive compositions for use in other packaging and structural applications.
  • the block copolymers useful herein are comprised of styrene and butadiene blocks arranged in a substantially radial configuration and contain 35%, and generally less than about 50% by weight of the styrene moiety. Of greater significance however, the copolymers selected should exhibit a modulus at 300% elongation of at least about 4.5 MPa and a solution viscosity less than about 1000 mPa.s (1000 cps) (25% in toluene at 23°C using a Brookfield viscometer). These copolymers may be prepared using methods taught, for example, in U.S. Pat. Nos.
  • the tackifying resins useful in the adhesive compositions can be hydrocarbon resins, hydrogenated hydrocarbons, synthetic polyterpenes, rosin esters, natural polyterpenes, and the like. More particularly, the useful tackifying resins include any compatible resins or mixtures thereof such as (1) natural and modified rosins such, for example, as gum rosin, wood rosin, tall oil rosin, distilled rosin, hydrogenated rosin, dimerized rosin, and polymerized rosin; (2) glycerol and pentaerythritol esters of natural and modified rosins, such, for example as the glycerol ester of pale, wood rosin, the glycerol ester of hydrogenated rosin, the glycerol ester of polymerized rosin, the pentaerythritol ester of hydrogenated rosin, and the phenolic-modified pentaerythritol ester of rosin; (3) copo
  • the remainder (up to about 60% by weight) of the hot melt adhesive comprises wax diluents.
  • Suitable waxes are the "petroleum derived waxes" which include both paraffin and microcrystalline waxes having melting points within the range of 54-107 °C (130-225°F) as well as synthetic waxes such as polyethylene and Fisher-Tropsch waxes which may be present, in addition to the paraffin wax, in levels of up to about 5% by weight.
  • stabilizers or antioxidants which may be included herein are high molecular weight hindered phenols and multifunctional phenols such as sulfur and phosphorous-containing phenols.
  • Hindered phenols are well known to those skilled in the art and may be characterized as phenolic compounds which also contain sterically bulky radicals in close proximity to the phenolic hydroxyl group thereof.
  • tertiary butyl groups generally are substituted onto the benzene ring in at least one of the ortho positions relative to the phenolic hydroxy group.
  • hindered phenols include: 1,3,5-trimethyl 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl)benzene; pentaerythrityl tetrakis-3(3,5-di-tert-butyl-4-hydroxyphenyl)propionate; n-octadecyl-3,5-di-tert-butyl-4-hydroxyphenol)-propionate; 4,4′-methylenebis (2,6-tert-butylphenol); 4,4′-thiobis (6-tert-butyl-o-cresol); 2,6-di-tertbutylphenol; 6-(4-hydroxyphenoxy)-2,4-bis(n-octyl-thio)
  • Optional additives may be incorporated into the hot melt compositions in order to modify certain properties thereof.
  • colorants such as titanium dioxide
  • fillers such as talc and clay, etc.
  • hot melt adhesive compositions may be formulated using techniques known in the art.
  • An exemplary procedure involves placing approximately 40% of the total tackifying resin concentration with all the wax and stabilizers in a jacketed mixing kettle, preferably in a jacketed heavy duty mixer, which is equipped with rotors and thereupon raising the temperature to a range of from 121 to 177 °C (250° to 350°F.), the precise temperature utilized depending on the melting point of the particular tackifying resins.
  • stirring is initiated and the block polymer is added. Mixing and heating are continued until a smooth, homogeneous mass is obtained whereupon the remainder of the tackifying resin is thoroughly and uniformly admixed therewith.
  • the resultant hot melt adhesives are generally produced in slat form and packaged in boxes.
  • the adhesives disclosed herein may be employed to bind a plurality of sheets in a wide range of bookbinding operations. Thus, they may be used in the binding of hard or soft bound books, sewn or unsewn books using one or two-shot (i.e., primed or unprimed) perfect binding or burst binding techniques.
  • the toughened adhesives described herein may also be effectively utilized in a variety of packaging and carton sealing applications.
  • Sample A was prepared using 35 parts Kraton D1122X, 35 parts Escorez 7312 (a petroleum hydrocarbon resin from Exxon Chemicals), 25 parts paraffin wax and 1-2 parts antioxidant.
  • Kraton D1122X is a styrene butadiene copolymer available from Shell Chemical containing 37% styrene and having a modulus of 4.8 MPa and a solution viscosity of 670 mPa.s (670 cps).
  • Sample B was prepared as sample A but substituting Europrene Sol T162 LW/1 for the Kraton and using 30 parts wax.
  • Sol T 162 LW/1 is a styrene butadiene block copolymer from Eni Chem Americas containing 40% styrene and having a modulus of 5.0 MPa and a solution viscosity of 750 mPa.s (750 cps).
  • Sample C (comparative) was prepared as sample B but substituting Europrene Sol T 168, a styrene butadiene block copolymer containing 43% styrene and having a modulus of 2.2 MPa and a Brookfield viscosity of 1000 mPa.s (1000 cps).
  • Viscosity measurements were determined using a Brookfield viscometer (Spindle 27) at 177 °C (350°F).
  • Tensile The tensile strength of a hot melt adhesive is determined on films cast from the hot melts according to Test Method A of ASTM procedure D 882-61T utilizing an Instron Tensile Tester, the films having been prepared according to the method set forth in the above described Film Cold Crack Test. The force required to start to stretch the specimen is recorded as the "tensile yield", the force required to break the specimen as "tensile break”. This procedure also provides a measurement of % elongation, which is the percentage stretch of the hot melt film at the point of rupture in obtaining the ultimate tensile strength.
  • Samples A and B containing the copolymers described herein provided properties superior to those achieved with the current commercially superior utilized block copolymers. Note, in particular, the improved Tensile Break and Cold Crack properties.
  • the following example illustrates the use of varying amounts of the raw materials in adhesive compositions of the invention and also provides a comparison with Stereon 840A, a commercially styrene butadiene block copolymer containing 43% styrene and having a modulus of 2.4 MPa and a viscosity of 650 mPa.s (650 cps).
  • Stereon 840A a commercially styrene butadiene block copolymer containing 43% styrene and having a modulus of 2.4 MPa and a viscosity of 650 mPa.s (650 cps).
  • Sample D was prepared by repeating the procedure of Example I using 37.5 parts Kraton D1122X, 37.5 parts Escorez 7312, 26.0 parts paraffin wax and 1.2 parts stabilizer.
  • Sample E was prepared as D but using Sol T162 LW/1 while Sample F was the comparative example which contained Stereon 840A.
  • Example I The procedure of Example I was again repeated to compare the performance of adhesives formulated with Kraton D1122X with one formulated with Kraton 1102, a linear styrene-butadiene copolymer containing 28% styrene, having a modulus of 2.76 MPa and a solution viscosity of 1200 mPa.s (1200 cps) (at 25 °C (77°F) in a a 25% toluene solution).
  • Sample G was formulated using 33.7 parts Kraton D1122X, 38.6 parts Escorez 7312, 27.7 parts paraffin wax and 1.2 parts stabilizer.
  • Sample H contained 33.7 parts Kraton 1102, 38.6 parts Escorez 7312, 29,7 parts paraffin wax and 1.2 parts stabilizer.
  • This example illustrates the use of different types of tackifing resins in the adhesive compositions of the invention.
  • Samples J, K and L were prepared using 37.5 parts Kraton DX1122X, 35.0 parts tackifier, 27.5 parts wax and 1.2, 1.0 and 1.0 parts, respectively, of stabilizer.
  • Escorez 7312 an aromatic resin from Exxon
  • Sample J used a pentaerythritol ester of rosin
  • Sample K used Nirez M 105 (an aromatic modified terpene resin from Reichold Chemical).
  • Hot melt ahdesive compositions were prepared as in Example I using a ratio of 43.75 parts copolymer to 56.25 parts aromatic tackifying resin and sufficient wax to bring the viscosity of the products to between 6000 and 8000 mPas.s (6000 and 8000 cps) at 177°C (350°F).
  • Sample L contained Sol T162 LW/1; Sample M, Kraton D1122; and Sample N, the comparative Sol T 162.
  • compositions were tested for tensile strength as described previously (results represent the tensile break value). In addition, they were tested for adhesion to primed book edges as favorite in many industrial book binding operations.
  • the hot melt adhesive was applied on top of a dried film of a conventional ethylene vinyl acetate emulsion primer, allowed to solidify, conditioned for 16 hours at 22 °C (72°F), 50% relative humidity and peeled off using an Instron Test machine. The test results are shown below:
  • the hot melt adhesive composition prepared from the Sol T162 does not exhibit adequate adhesion to be used in applications requiring the toughned hot melt compositions of the present invention.
  • Adhesives similar to those described in Examples I-V were prepared and tested for the additional properties of flexibility required in hot melt adhesive compositions used in book binding. In these cases, relatively heavy coatings of the adhesive are applied to the bound edges of the book block and a paper cover affixed thereto. Due to the heavy coating weight and the insulating properties of the book block, cooling proceeds rather slowly and a specific crystalline type structure is formed. This structure is simulated by forming samples of the adhesive in disks approximately 4 mm thick and allowing them to solidify at room temperature. After aging for 24 hours, the samples are placed in a clamp held at approximately 180° angle for 24 hours. The degree of flexibility of the adhesive is noted by the presence or absence of stress cracks or fractures in the sample after removal of the clamps and blending the specimen back flat.
  • adhesives were prepared from the rubbery copolymer, tackifier resins and wax using 100 parts of the copolymer/resin mixture and varying parts paraffin wax. Since the wax content is a diluent, only the ratio of copolymer to resins will be discussed in the examples.
  • Adhesive samples were prepared using commercially employed formulations with Sol T168 in copolymer/resin ratio of 48.3/51.7;50/50 and 53.2/46.8. Only the latter sample containing 53.2 parts SOL T 168 copolymer passed the stress crack test. In contrast, similar adhesives were formulated using 50/50 ratios of Kraton 1122X to resin and Sol T162LW/1 to resin. No cracking was observed. As a further comparison, another sample was prepared with a 50/50 ratio of Stereon 840A to resin. The latter sample failed the stress crack test.
  • the following example illustrates the preparation of a hot melt adhesive composition suitable for packaging applications.
  • a hot melt adhesive was prepared using the basic procedure of Example I with 25 parts Kraton D1122X, 25 parts of a terpene phenolic resin, 50 parts paraffin wax and 1 part stabilizer.
  • the adhesive When tested as described above, the adhesive had a viscosity of 375 mPa.s (375 cps) at 177°C (350°F); 875 mPa.s (875 cps) at 149 °C (300°F); a tensile yield of 3.2 MPa; a tensile break of 3.5 MPa; an elongation of 860% and a film cold crack of -29, -26°C (-20°, -15°F).
  • Peel Temperature Test A bead of test adhesive approximately 3 mm (1/8 inch) in diameter is applied at 177 °C (350°F) with a glass rod onto 98g/m2 (60 pound/ream) kraft paper. A second sheet of the same paper is placed in direct alignment with the first sheet within 2 seconds and pressed thereto to form a kraft-to-kraft bond.
  • the bonded sheets are then cut perpendicular to the adhesive line into 1 inch wide strips.
  • Duplicate bonded specimens are placed in an oven with one free end of the specimen attached to a fixed support and a 100 gram load suspended from the other free end. The oven temperature is then increased in 5,6 °C (10°F) increments at 15 minute intervals. The temperature at which bond delamination occurred is specified as the peel temperature.
  • Shear Temperature Test Samples are prepared as in peel temperature test but opposite ends of the bonded specimen are suspended and weighted to stress the bond in a shear mode. Temperature of oven is increased as in peel test until failure.
  • the adhesive gave a peel value of 66 °C (150°F) and a shear value of 77 °C (170°F).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Claims (10)

  1. Schlagfeste Heißschmelzklebstoffzusammensetzung umfassend:
    a) 10 bis 40 Gew.% eines im wesentlichen radialen Styrol-Butadien-Blockcopolymers mit einem Styrolgehalt von mindestens 35 Gew.%, einem Modul bei 300% Dehnung von mindestens 4,5 mPa und einer Lösungsviskosität von weniger als etwa 1000 mPa.s (1000 cps);
    b) 20 bis 65 Gew.% eines kompatiblen klebrigmachenden Harzes;
    c) 0,1 bis 4 Gew.% eines Stabilisators; und
    d) als Rest der Zusammensetzung (auf insgesamt 100%) mindestens ein Wachsverdünnungsmittel und wahlweise weitere andere Additive.
  2. Klebstoff nach Anspruch 1, wobei das Styrol-Butadien-Blockcopolymer 37 bis 40% Styrol enthält, ein Modul bei 300% Dehnung von 4,6 bis 5 mpa und eine Lösungsviskosität von 640 bis 750 mpa.s (640 bis 750 cps) besitzt.
  3. Klebstoff nach Anspruch 1, wobei das klebrigmachende Harz ausgewählt ist aus der Gruppe bestehend aus natürlichen und modifizierten Harzölen, Glycerol- und Pentaerythritestern der natürlichen und modifizierten Harzöle, Copolymeren und Terpolymeren von natürlichen Terpenen, Polyterpenharzen mit einem Erweichungspunkt - bestimmt nach der ASTM-Methode E28-58T - von 80 bis 150°C, phenolisch modifizierten Terpenharzen und hydrierten Derivaten davon, aliphatischen Mineralöl-Kohlenwasserstoffharzen mit einem Kugel- und Ring-Erweichungspunkt von ca. 70 bis 135°C, aromatischen Mineralöl-Kohlenwasserstoffharzen und hydrierten Derivaten davon sowie alicyclischen Mineralöl-Kohlenwasserstoffharzen und hydrierten Derivaten davon.
  4. Klebstoff nach Anspruch 1, wobei das Wachs Paraffin oder mikrokristallines Wachs ist.
  5. Klebstoff nach Anspruch 1, wobei zusätzlich bis zu 5 Gew.% Fischer-Tropsch-Wachs vorliegen.
  6. Verfahren zum Binden von Büchern, wobei ein Heißschmelzklebstoff auf eine Vielzahl von Blättern am Buchrücken aufgebracht wird, gekennzeichnet durch die Verwendung einer Zusammensetzung nach Anspruch 1 als Heißschmelzklebstoff.
  7. Verfahren nach Anspruch 6, wobei in der Klebstoffzusammensetzung zusätzlich bis zu 5 Gew.% Fischer-Tropsch-Wachs vorliegen.
  8. Verfahren nach Anspruch 6, wobei der Buchrücken vor der Anwendung des Heißschmelzklebstoffs mit einem Primer vorbereitet wird.
  9. Buch mit einer Vielzahl von Blättern, die am Rücken mit Hilfe einer verfestigten Heißschmelzklebstoffzusammensetzung nach Anspruch 1 miteinander gebunden sind.
  10. Buch nach Anspruch 9, wobei in der Klebstoffzusammensetzung zusätzlich bis zu 5 Gew.% eines Fischer-Tropsch-Wachses vorliegen.
EP89113908A 1988-08-17 1989-07-27 Schlagfesten Kautschuk enthaltende Schmelzklebstoffzusammensetzungen für die Buchbinderei Expired - Lifetime EP0356712B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US233171 1988-08-17
US07/233,171 US4942195A (en) 1988-08-17 1988-08-17 Toughened rubber based hot melt adhesive compositions for bookbinding applications

Publications (2)

Publication Number Publication Date
EP0356712A1 EP0356712A1 (de) 1990-03-07
EP0356712B1 true EP0356712B1 (de) 1993-01-13

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EP89113908A Expired - Lifetime EP0356712B1 (de) 1988-08-17 1989-07-27 Schlagfesten Kautschuk enthaltende Schmelzklebstoffzusammensetzungen für die Buchbinderei

Country Status (6)

Country Link
US (1) US4942195A (de)
EP (1) EP0356712B1 (de)
JP (1) JPH0717882B2 (de)
CA (1) CA1314643C (de)
DE (1) DE68904382T2 (de)
DK (1) DK403489A (de)

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US6034159A (en) * 1995-01-06 2000-03-07 H.B. Fuller Licensing & Financing, Inc. Fast setting multipurpose bookbinding adhesive with excellent flexibility
JP2986016B2 (ja) 1996-06-19 1999-12-06 エイチ・ビー・フラー・ライセンシング・アンド・ファイナンシング・インコーポレイテッド 反応性ホットメルトポリウレタン接着剤を用いた本のためのカバーおよびかかるカバーを含む本
CA2255793A1 (en) * 1996-07-12 1998-01-22 H.B. Fuller Licensing & Financing, Inc. Low application temperature hot melt with excellent heat and cold resistance
US6359075B1 (en) 2001-01-09 2002-03-19 Bridgestone/Firestone, Inc. Means of producing high diblock content thermoplastic elastomers via chain transfer
US6417270B1 (en) 2001-01-09 2002-07-09 Firestone Polymers, Llc Means of producing high diblock content thermoplastic elastomers with functional termination
US20040180197A1 (en) * 2003-03-13 2004-09-16 Everaerts Albert I. Closure systems with self-adhering adhesives, and articles
US7579394B2 (en) * 2007-01-16 2009-08-25 Xerox Corporation Adhesion promoter
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US8357763B2 (en) * 2007-05-02 2013-01-22 Xerox Corporation Adhesion promoter
US8829105B2 (en) 2012-01-18 2014-09-09 Eastman Chemical Company Low molecular weight polystyrene resin and methods of making and using the same
WO2015135113A1 (en) 2014-03-10 2015-09-17 Henkel (China) Company Limited Hot melt adhesive composition for bookbinding
CN111320763B (zh) * 2018-12-14 2022-12-02 科建高分子材料（上海）股份有限公司 一种防止热熔胶产生颗粒的生产工艺

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Also Published As

Publication number Publication date
CA1314643C (en) 1993-03-16
DE68904382D1 (de) 1993-02-25
DK403489D0 (da) 1989-08-16
US4942195A (en) 1990-07-17
DE68904382T2 (de) 1993-05-06
JPH0275680A (ja) 1990-03-15
EP0356712A1 (de) 1990-03-07
JPH0717882B2 (ja) 1995-03-01
DK403489A (da) 1990-02-18

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